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Cyanide Copper Plating

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Cyanide Copper Plating Jack Horner Applications A relatively new application with which most everyone Electroplated copper from cyanide-based plating solutions has daily contact is found in coinage, where cyanide copper has long been used both as an engineering or decorative is used to plate zinc alloy penny blanks by the millions! The finish, and as an undercoat for other plated metals. These properties of the unbrightened cyanide copper deposits are cyanide copper solutions are used to plate on a wide variety such that the coining operation produces a very bright appear- of base materials. These include steels, zinc alloys, aluminum ance. The plated penny has surprised many critics with its alloys, copper alloys, magnesium alloys, nickel alloys, and resistance to corrosion during the rigors of circulation. lead alloys. An important property of copper from cyanide- Copper is used in many other plating applications in which based systems is its ability to adhere well to these alloys. cyanide solutions are used very little. Electroforming, with a Other properties of electroplated copper deposits that are of few exceptions, is usually done from acid copper solutions. interest for various applications include: (a) soft, ductile Printed wiring boards utilize electroless copper, acid copper deposits; (b) it is easily buffed; (c) good electrical conductiv- and pyrophosphate copper, with the exception of one major ity; (d) good solderability; (e) stop-off properties on steel for manufacturer who used cyanide copper successfully on spe- selective case-hardening processes; (f) decorative finishes cial boards for many years. Copper plate is also used as a dry can be plated bright with proprietary additives, or given lubricant in some wire drawing processes, but an immersion attractive antique finishes such as oxides or patinas, (g) copper process from acid solutions is most often mentioned. copper plate from cyanide plating solutions protects acid- Immersion copper deposits are also used in coating steel sensitive base metals from attack by subsequent acid plating items such as BB shot for appearance, lubricity, and tempo- solutions; and (h) it plates easily with other metals. rary rust prevention; on welding rods for low contact resis- As an undercoat for subsequent nickel-and-chromium or tance; and on other steel parts, sometimes just for color nickel-and-brass electroplates, cyanide copper is applied in identification purposes. the decorative or functional plating of zinc alloy castings used for trim or hardware in the automotive, appliance, electrical, Processes plumbing fixtures, household goods and other industries. Copper is electroplated primarily from cyanide, acid sulfate Copper is also used as an undercoat over copper and nickel or pyrophosphate plating solutions; in the U.S., pyrophos- alloys for subsequent nickel-and-gold, silver, or nickel-and- phate is the least used. Other bath formulations have been silver electroplates in the electronic connector and electrical published or advertised but have not reached sufficient com- industries. mercial volume to be significant. Since soft copper is much easier to polish by buffing than steel, cyanide copper plated deposits can be plated on rougher Cyanide or Acid? steels and then buffed to produce “high-luster” finishes when While it is not the intent here to go into all the factors that used as an undercoat for a minimum thickness of subsequent influence the choice of which copper plating solution to use, bright nickel plating. a list of the major factors would include: As a decorative finish without subsequent electroplates of 1. Acid copper plating solutions attack most basis metals other metals, copper cyanide deposits are used on cabinet and/or produce immersion deposits with poor adhesion, hardware, hinges, drawer pulls, knobs and brackets. These especially on steel, zinc and aluminum alloy substrates. are sometimes given post-treatments to color or darken the When acid copper is to be plated over these metals, deposits, which are then highlighted by mechanical finishing cyanide copper plating is used as an undercoat to produce or selective buffing to produce antique finishes. Similar good adhesion. finishes are found on fireplace trim, lamps, lighting fixtures 2. Deposits from cyanide plating solutions exhibit much less and other household items with or without the antique post- deposit thickness variations (better throwing power) over treatment. For these applications, clear lacquers are used over the surface of a part. The more complicated the shape of a the copper plate to preserve the color and luster. part, the more significant this property becomes. Some functional applications for cyanide copper as a finish 3. Cyanide is, of course, highly poisonous and must be include plating the steel clamps on battery jumper cables, as handled with great care. Additionally, limitations on al- well as other electrical connectors and fittings, alligator clips, lowable cyanide in wastewaters are very stringent and etc. Aluminum buss bars have been plated with cyanide complete destruction methods are required in most areas. copper to provide low contact resistance for bolted connec- However, it should be recognized that cyanide destruction tions. Lead sporting ammunition is plated with heavy copper technology is well established and proven effective. deposits to prevent lead fouling of gun barrels, protect the 4. Proprietary bright acid copper solutions are capable of a projectile shape, and produce desired expansion characteris- high degree of “leveling” i.e., the smoothing of rough tics on impact. surfaces with increased plating thickness). Cyanide cop- 36 PLATING & SURFACE FINISHING per solutions generally produce the opposite effect, espe- caustic soda. A concentration of 2 to 4 oz/gal of Rochelle salts cially on rougher surfaces; however, periodic current or an equivalent proprietary additive also helps. For applica- reversal (PR) cycles and/or pulse plating with some pro- tions involving steel, 2 oz/gal caustic can be used. For use prietary additives can provide significant leveling. over zincated aluminum, omit the caustic and lower the pH to 9.8 to 10.2 with sodium bicarbonate. Strike at a current Cyanide Copper Plating Solutions Components density of 10 to 25 A/ft2 for 2 to 3 min. at 110 to 120 °F, then Copper cyanide, the source of copper in solution, is not transfer directly to the plating tank without a water rinse. soluble in water. It requires either sodium or potassium Filter continuously to avoid roughness problems. cyanide to form the soluble complexes to put it into solution. Formulations for copper plating solutions vary according Further, an excess of the alkali metal cyanide, over the to use. High speed solutions for rack plating contain 5 to 10 amount necessary to form the complexes, is needed for oz/gal copper (nominally about 6 oz/gal). Free cyanide is an sound, good quality deposits and good anode corrosion. This important component and is maintained proportionally to the excess amount is referred to as “free” cyanide or copper, usually at a 2:1 copper to “free” potassium cyanide “uncomplexed” cyanide. Caustic soda (sodium hydroxide) or ratio. Low free cyanide solutions give improved plating caustic potash (potassium hydroxide) is added to: (1) in- efficiency and higher speed; however, anode corrosion is crease conductivity, (2) reduce electrochemical attack on reduced and deposits may be rough. Caustic potash (potas- steel anode containers or any wetted exposed steel, and (3) sium hydroxide) at 2 to 4 oz/gal and Rochelle salts at 5 to 6 reduce the decomposition of cyanide. Caustic additions also oz/gal make up the remainder of the basic bath. Anodes must have an influence on anode films. Rochelle salts or propri- corrode effectively to keep roughness and cyanide oxidation etary additives are commonly used. They provide a finer- minimal. Proper anode current density range is important. If grained copper deposit, as well as improving anode corro- anodes are bagged, bag weave size is critical and the bagged sion. In addition, they limit the effects of detrimental metallic anode area should be as large as possible. impurities. For barrel plating, solutions vary in concentration from One other chemical found in cyanide copper plating solu- plant to plant. Some platers use high copper, up to 8 to 10 oz/ tions is the alkali metal carbonate. A small amount (2 to 4 oz/ gal. When barrel plating parts that nest or stick together gal) is sometimes added to new solutions to provide solution excessively, higher free cyanide can be helpful; a 1.5:1 buffering in the cathode film and improved conductivity. In copper to free cyanide ratio may be used. any case, carbonates are formed naturally in the solution with Proprietary additives are widely used in cyanide copper time, due to the decomposition of cyanide and absorption of plating solutions. These additives improve the color, yield carbon dioxide from the air. (This is a strong argument semi-bright or fully bright deposits, control the effects of against air agitation of the solution with in-plant air.) Even- various impurities, and improve anode corrosion. Brighten- tually, with no drag-out losses, or by using poorly corroding ers may be metallic, organic, or mixtures. Generally, organic copper anodes or insoluble anodes, or both, carbonates will brighteners do not produce as bright a deposit, but after build up to an excessive amount and have to be removed subsequent bright nickel plating, the deposit appears no
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